Theoretical study of spectroscopy, interaction, and dissociation of linear and T-shaped isomers of RgClF (Rg = He, Ne, and Ar) van der Waals complexes

Abstract

Spectroscopy, interaction energy, and dissociation of linear and T-shaped isomers of HeClF, NeClF, and ArClF van der Waals complexes in their ground state have been studied in detail using MP2 and CCSD(T) methods in conjunction with correlation consistent valence triple and quadruple zeta basis sets. A method, called potential method, has been developed to remove the discrepancy between theoretical and experimental values for the depth of the potential well and dissociation energies for these complexes. This is also supported by the supermolecular approach. Most of the structural and spectroscopic properties of these complexes are first reported and the rest agree very well with the experimental and theoretical values wherever available. Two local minima corresponding to linear and asymmetric T-shaped are found for RgClF complexes. For NeClF complex, the predicted values for the equilibrium bond length and well depth are R _NeCl = 3.096 Å and \( D_{\text{e}}^{\text{p}} \) = 161.50 cm⁻¹ for the linear isomer and R _NeCl = 3.503 Å and \( D_{\text{e}}^{\text{p}} \) = 126.10 cm⁻¹ for the T-shaped isomer. Various dissociation channels are also investigated in detail.